TW201816060A - Polishing agent, polishing method, and liquid additive for polishing - Google Patents

Polishing agent, polishing method, and liquid additive for polishing Download PDF

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TW201816060A
TW201816060A TW106129934A TW106129934A TW201816060A TW 201816060 A TW201816060 A TW 201816060A TW 106129934 A TW106129934 A TW 106129934A TW 106129934 A TW106129934 A TW 106129934A TW 201816060 A TW201816060 A TW 201816060A
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polishing
abrasive
oxide particles
mass
acid
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TW106129934A
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TWI773685B (en
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小林元気
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日商旭硝子股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/06—Other polishing compositions
    • C09G1/14—Other polishing compositions based on non-waxy substances
    • C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Composite Materials (AREA)
  • Disintegrating Or Milling (AREA)

Abstract

The present invention relates to a polishing agent including: metal oxide particles; an organic acid having a monodentate ligand; a nonionic polymer; and water, in which the polishing agent has a pH of from 3.0 to 7.0, and the nonionic polymer includes at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether and polyoxypropylene polyglyceryl ether.

Description

研磨劑及研磨方法、與研磨用添加液Abrasive, polishing method, and polishing additive

本發明係關於一種研磨劑及研磨方法、與研磨用添加液，尤其是關於一種用以半導體積體電路之製造中之化學機械研磨之研磨劑、與使用該研磨劑之研磨方法、及用以製備研磨劑之研磨用添加液。The present invention relates to an abrasive and a polishing method, and an additive for polishing, and more particularly, to an abrasive for chemical mechanical polishing in the manufacture of semiconductor integrated circuits, a polishing method using the abrasive, and An abrasive additive polishing solution is prepared.

近年來，隨著半導體積體電路之高積體化或高功能化，用以半導體元件之微細化及高密度化之微細加工技術之開發不斷發展。自先前以來，為了於半導體積體電路裝置(以下，亦稱為半導體元件)之製造中防止層表面之凹凸(階差)超過微影法之焦點深度而變得無法獲得充分之解像度等問題，而使用化學機械研磨法(Chemical Mechanical Polishing：以下稱為CMP)以使層間絕緣膜或嵌入配線等平坦化。利用CMP之高平坦化之重要性係隨著元件之高精細化或微細化之要求變嚴格而越發增大。 又，近年來，為了於半導體元件之製造中推進半導體元件之更高度之微細化，而導入元件隔離寬度較小之利用淺溝槽之隔離法(Shallow Trench Isolation：以下稱為STI)。 STI係於矽基板形成溝槽(trench)，並於溝槽內嵌入絕緣膜，藉此形成電氣絕緣之元件區域之方法。於STI中，首先如圖1(a)所示般，利用氮化矽膜2等將矽基板1之元件區域遮蔽後，於矽基板1形成溝槽3，以掩埋溝槽3之方式堆積二氧化矽膜4等絕緣膜。其次，藉由CMP，使作為凹部之溝槽3內之二氧化矽膜4殘留，並且將作為凸部之氮化矽膜2上之二氧化矽膜4研磨去除，藉此獲得如圖1(b)所示般於溝槽3內嵌入有二氧化矽膜4之元件隔離構造。 關於此種STI中之CMP，其可藉由提高二氧化矽膜與氮化矽膜之選擇比(意指二氧化矽膜之研磨速度與氮化矽膜之研磨速度之比。以下亦簡稱為選擇比)，而於氮化矽膜露出之時點停止研磨之進行。以上述方式使用氮化矽膜作為擋止膜之研磨方法與通常之研磨方法相比，可獲得更平滑之面。 如上所述，關於近年來之CMP技術，就成本方面而言，不僅要求對二氧化矽膜之較高之研磨速度，上述選擇比之大小亦變得重要。 因此，提出有配合此種要求特性而改善研磨劑之研磨特性之方法。專利文獻1中揭示有含有氧化鈰粒子等作為研磨粒，並含有多牙配位基之有機酸、多元醇化合物、或其衍生物之硬碟基板用、或半導體基板用研磨劑。 然而，關於專利文獻1及專利文獻2中所示之研磨劑，即便確保研磨速度為一定程度較高之值，氮化矽膜之研磨速度之抑制亦不充分，因此不可謂二氧化矽膜與氮化矽膜之選擇比充分高。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2000-160142號公報 [專利文獻2]日本專利特開2006-278773號公報In recent years, as semiconductor integrated circuits have become highly integrated or highly functional, the development of microfabrication technology for miniaturization and high density of semiconductor devices has continued to develop. Since the past, in order to prevent the unevenness (step difference) on the surface of the layer from exceeding the depth of focus of the lithography method in the manufacture of semiconductor integrated circuit devices (hereinafter also referred to as semiconductor devices), it has become impossible to obtain sufficient resolution, On the other hand, chemical mechanical polishing (hereinafter referred to as CMP) is used to planarize the interlayer insulating film, the embedded wiring, and the like. The importance of high planarization using CMP is increasing as the requirements for high definition or miniaturization of devices become stricter. In addition, in recent years, in order to promote further miniaturization of semiconductor devices in the manufacture of semiconductor devices, a shallow trench isolation method (hereinafter referred to as STI) using a shallow trench isolation has been introduced to reduce the isolation width of the devices. STI is a method of forming a trench on a silicon substrate and embedding an insulating film in the trench, thereby forming an electrically insulating element region. In STI, as shown in FIG. 1 (a), a silicon nitride film 2 or the like is used to mask the element area of the silicon substrate 1. Then, a trench 3 is formed on the silicon substrate 1, and the trench 3 is buried. Insulating film such as silicon oxide film 4. Next, by CMP, the silicon dioxide film 4 in the trench 3 as the concave portion is left, and the silicon dioxide film 4 on the silicon nitride film 2 as the convex portion is polished and removed, thereby obtaining FIG. 1 ( b) A device isolation structure with a silicon dioxide film 4 embedded in the trench 3 as shown. Regarding the CMP in this STI, it can be achieved by increasing the selection ratio of the silicon dioxide film to the silicon nitride film (meaning the ratio of the polishing speed of the silicon dioxide film to the polishing speed of the silicon nitride film. It is also referred to as simply Selection ratio), and polishing is stopped when the silicon nitride film is exposed. The polishing method using the silicon nitride film as the stopper film in the above manner can obtain a smoother surface than the conventional polishing method. As mentioned above, regarding the CMP technology in recent years, in terms of cost, not only a higher polishing speed for the silicon dioxide film is required, but also the magnitude of the above-mentioned selection ratio becomes important. Therefore, a method has been proposed to improve the polishing characteristics of the abrasive in accordance with such required characteristics. Patent Document 1 discloses an abrasive for a hard disk substrate or a semiconductor substrate containing an organic acid, a polyhydric alcohol compound, or a derivative thereof containing cerium oxide particles and the like as abrasive particles and containing a multidentate ligand. However, regarding the abrasives shown in Patent Documents 1 and 2, even if the polishing rate is ensured to a certain high value, the suppression of the polishing rate of the silicon nitride film is insufficient, so it cannot be said that the silicon dioxide film and the The selection ratio of the silicon nitride film is sufficiently high. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2000-160142 [Patent Literature 2] Japanese Patent Laid-Open No. 2006-278773

[發明所欲解決之問題] 本發明係為了解決上述問題而完成者，其目的在於提供一種例如於CMP、尤其是STI中之包含氧化矽面之被研磨面之CMP中，可維持對如二氧化矽膜之氧化矽膜之充分高之研磨速度，並且將對氮化矽膜之研磨速度抑制為較低，而達成較高之選擇比與良好之平坦性之研磨劑、研磨方法、及研磨用添加液。 [解決問題之技術手段] 本發明之研磨劑之特徵在於：其係含有金屬氧化物粒子、具有單牙配位基之有機酸、非離子性聚合物、及水，且pH值為3.0以上且7.0以下者，上述非離子性聚合物包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。 於本發明之研磨劑中，上述具有單牙配位基之有機酸較佳為選自由具有雜環之單羧酸、碳數4以上且具有羥基之單羧酸、及具有胺基之單羧酸所組成之群中之至少1種。上述金屬氧化物粒子較佳為氧化鈰粒子。 關於上述具有單牙配位基之有機酸之含有比率，相對於研磨劑之總質量較佳為0.003質量%以上且1.0質量%以下。關於上述非離子性聚合物之含有比率，相對於研磨劑之總質量較佳為0.0002質量%以上且2.0質量%以下。上述金屬氧化物粒子之平均二次粒徑較佳為10 nm以上且500 nm以下。關於上述金屬氧化物粒子之含有比率，相對於研磨劑之總質量較佳為0.01質量%以上且10.0質量%以下。 本發明之研磨方法係一面供給研磨劑一面使被研磨面與研磨墊接觸，藉由兩者之相對運動而進行研磨者，其特徵在於使用本發明之研磨劑作為上述研磨劑，而對半導體基板之含有包含氧化矽之面之被研磨面進行研磨。 本發明之研磨用添加液之特徵在於：其係用以與金屬氧化物粒子之分散液進行混合而製備研磨劑之添加液，該添加液含有具有單牙配位基之有機酸、非離子性聚合物、及水，且pH值為3.0以上且7.0以下，並且上述非離子性聚合物包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。 於本發明之研磨用添加液中，上述具有單牙配位基之有機酸較佳為選自由具有雜環之單羧酸、碳數4以上且具有羥基之單羧酸、及具有胺基之單羧酸所組成之群中之至少1種。 再者，於本發明中，所謂「被研磨面」，係指研磨對象物之被研磨之面，例如意指表面。於本說明書中，「被研磨面」亦包括於製造半導體元件之過程中出現在半導體基板之中間階段之表面。 進而，於本發明中，「氧化矽」具體而言為二氧化矽，但並不限定於此，設為亦包含二氧化矽以外之矽氧化物者。 [發明之效果] 根據本發明之研磨劑及研磨方法，例如於CMP、尤其是STI中之包含氧化矽面之被研磨面之CMP中，可維持對氧化矽膜之充分高之研磨速度，並且將對氮化矽膜之研磨速度抑制為較低，而達成氧化矽膜與氮化矽膜之高選擇比。[Problems to be Solved by the Invention] The present invention has been made in order to solve the above problems, and its purpose is to provide, for example, a CMP, especially a CMP including a polished surface including a silicon oxide surface in STI, which can maintain the same The silicon oxide film has a sufficiently high polishing speed of the silicon oxide film, and the polishing speed of the silicon nitride film is suppressed to be low, and an abrasive, a polishing method, and a polishing having a high selection ratio and good flatness are achieved. With additive solution. [Technical means to solve the problem] The abrasive of the present invention is characterized in that it contains metal oxide particles, an organic acid having a single-dentate ligand, a nonionic polymer, and water, and has a pH value of 3.0 or more and Below 7.0, the non-ionic polymer includes at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether. In the abrasive of the present invention, the organic acid having a monodentate ligand is preferably selected from a monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having 4 or more carbon atoms and a hydroxyl group, and a monocarboxylic acid having an amine group. At least one member of the group of acids. The metal oxide particles are preferably cerium oxide particles. The content ratio of the organic acid having a single-dentate ligand is preferably 0.003 mass% or more and 1.0 mass% or less with respect to the total mass of the abrasive. The content ratio of the non-ionic polymer is preferably 0.0002% by mass or more and 2.0% by mass or less with respect to the total mass of the abrasive. The average secondary particle diameter of the metal oxide particles is preferably from 10 nm to 500 nm. The content ratio of the metal oxide particles is preferably 0.01% by mass or more and 10.0% by mass or less with respect to the total mass of the abrasive. The polishing method of the present invention is one in which the surface to be polished is brought into contact with the polishing pad while the abrasive is supplied, and the relative polishing is performed by the relative movement of the two. The polished surface containing the surface containing silicon oxide is polished. The grinding additive liquid of the present invention is characterized in that it is an additive liquid for preparing an abrasive by mixing with a dispersion liquid of metal oxide particles, and the additive liquid contains an organic acid having a single-dentate ligand, and is nonionic. Polymer and water, and the pH value is 3.0 or more and 7.0 or less, and the non-ionic polymer contains at least 1 selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether Species. In the polishing additive of the present invention, the organic acid having a monodentate ligand is preferably selected from a monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having 4 or more carbon atoms and a hydroxyl group, and an amino group having an amine group. At least one of the group consisting of a monocarboxylic acid. Furthermore, in the present invention, the "surface to be polished" refers to the surface to be polished of the object to be polished, for example, the surface. In this specification, the "surface to be polished" also includes a surface that appears at an intermediate stage of a semiconductor substrate in the process of manufacturing a semiconductor element. Furthermore, in the present invention, the "silicon oxide" is specifically silicon dioxide, but it is not limited thereto, and it is assumed that silicon oxide other than silicon dioxide is also included. [Effect of the Invention] According to the polishing agent and polishing method of the present invention, for example, in a CMP, particularly a CMP of a polished surface including a silicon oxide surface in an STI, a sufficiently high polishing rate for a silicon oxide film can be maintained, and The polishing rate of the silicon nitride film is suppressed to be low, and a high selection ratio of the silicon oxide film and the silicon nitride film is achieved.

以下，對本發明之實施形態進行說明。本發明並不限定於以下之實施形態，只要符合本發明之主旨，則其他實施之形態亦可屬於本發明之範疇。 ＜研磨劑＞ 本發明之研磨劑之特徵在於：其係含有金屬氧化物粒子、具有單牙配位基之有機酸、非離子性聚合物、及水，且pH值為3.0以上且7.0以下者，非離子性聚合物包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。以下，亦將包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種之非離子性聚合物稱為非離子性聚合物(P)。 於將本發明之研磨劑例如用於STI中之包含氧化矽膜(例如二氧化矽膜)之被研磨面之CMP之情形時，對氧化矽膜具有較高之研磨速度，而且對氮化矽膜之研磨速度充分低，而可達成氧化矽膜與氮化矽膜之高選擇比。而且，可實現平坦性較高之研磨。 關於本發明之研磨劑發揮如上述般優異之研磨特性之機制，尚未明確，但認為其原因在於：包含具有單牙配位基之有機酸與具有特定分子結構之非離子性聚合物(P)兩者。即，認為其原因在於：研磨劑所含有之具有單牙配位基之有機酸於上述具有特定分子結構之非離子性聚合物(P)之存在下，於pH值為3.0以上且7.0以下之區域中，經由該分子之末端基而靜電吸附於金屬氧化物粒子之表面及包含氧化矽膜之被研磨面。而且，認為將金屬氧化物粒子表面、與包含氧化矽膜之被研磨面之表面之狀態最佳化之結果為，不會損壞金屬氧化物粒子之分散性而獲得對氧化矽膜之較高之研磨速度、及氧化矽膜與氮化矽膜之高選擇比兩者。 以下，對本發明之研磨劑所含有之各成分、及pH值進行說明。 (金屬氧化物粒子) 本發明之研磨劑所含有之金屬氧化物粒子係具有作為研磨粒之功能者。作為金屬氧化物粒子，可列舉：氧化鈰、氧化鋁、二氧化矽、氧化鈦、氧化鋯等金屬氧化物之粒子。作為金屬氧化物粒子，就對氧化矽膜之研磨速度之高低而言，較佳為氧化鈰粒子。 於在本發明之研磨劑中，使用氧化鈰粒子作為金屬氧化物粒子之情形時，研磨劑所含有之氧化鈰粒子並無特別限定，例如可使用利用日本專利特開平11-12561號公報或日本專利特開2001-35818號公報中記載之方法所製造之氧化鈰粒子。即，可使用如下氧化鈰粒子，其係於硝酸鈰(IV)銨水溶液中加入鹼而製作氫氧化鈰凝膠，將對其進行過濾、清洗、焙燒而獲得之氧化鈰粒子、或高純度之碳酸鈰粉碎後進行焙燒，進而進行粉碎、分級而獲得。又，亦可使用如下氧化鈰粒子，其係如日本專利特表2010-505735號所記載般使鈰(III)鹽於液體中進行化學性氧化而獲得。 金屬氧化物粒子之平均粒徑較佳為10 nm以上且500 nm以下，更佳為30 nm以上且300 nm以下。若平均粒徑超過500 nm，則有於被研磨面產生刮痕等研磨損傷之虞。又，若平均粒徑未達10 nm，則不僅有研磨速度降低之虞，亦由於每單位體積之表面積之比率較大，故而容易受表面狀態之影響，且根據pH值或添加劑之濃度等條件而金屬氧化物粒子變得容易凝集。 如氧化鈰粒子之金屬氧化物粒子係於研磨劑中以一次粒子凝集而成之凝集粒子(二次粒子)的形式存在，因此將金屬氧化物粒子之較佳粒徑設為以平均二次粒徑表示者。即，金屬氧化物粒子較佳為平均二次粒徑為10 nm以上且500 nm以下，更佳為30 nm以上且300 nm以下。平均二次粒徑係使用分散於純水等分散介質中而成之分散液，使用雷射繞射、散射式等之粒度分佈計而進行測定。 金屬氧化物粒子之含有比率(濃度)相對於研磨劑之總質量，較佳為0.01質量%以上且10質量%以下。於金屬氧化物粒子之含有比率為0.01質量%以上且10質量%以下之情形時，獲得對氧化矽膜充分高之研磨速度。又，研磨劑之黏度亦不會過高而操作良好。金屬氧化物粒子之含有比率(濃度)更佳為0.025質量%以上且3.0質量%以下，尤佳為0.025質量%以上且1.0質量%以下。 金屬氧化物粒子亦可使用事先分散於介質中之狀態者(以下，稱為金屬氧化物粒子分散液)。作為介質，可較佳地使用水。 (水) 於本發明之研磨劑中，含有水作為使金屬氧化物粒子分散之介質，且作為使下述具有單牙配位基之有機酸及非離子性聚合物(P)溶解之介質。關於水之種類並無特別限定，但考慮對具有單牙配位基之有機酸及非離子性聚合物(P)之影響、雜質混入之防止、對pH值等之影響，較佳為使用純水、超純水、離子交換水等。 (具有單牙配位基之有機酸) 作為本發明之研磨劑所含有之具有單牙配位基之有機酸，較佳為單羧酸。作為單羧酸，較佳為選自具有雜環之單羧酸、碳數4以上且具有羥基之單羧酸、具有胺基之單羧酸中之至少1種。於以下例示列舉可較佳地用於本發明之研磨劑之單羧酸，但並不限定於其等。 作為具有雜環之單羧酸，可較佳地使用具有含有氮原子之雜環(含氮雜環)之單羧酸、或具有含有氮以外之雜原子之雜環之單羧酸。作為具有含有氮原子之雜環(含氮雜環)之單羧酸，例如可列舉：2-吡啶羧酸、3-吡啶羧酸、4-吡啶羧酸、吡羧酸、2-喹啉甲酸(喹哪啶酸)、吡咯啶酮羧酸、DL-焦麩胺酸、DL-2-哌啶甲酸等。 作為具有含有氮以外之雜原子之雜環之單羧酸，可列舉具有僅含有氧原子作為雜原子之雜環之單羧酸，具體而言，可列舉2-呋喃甲酸、3-呋喃甲酸、四氫呋喃-2-羧酸等。 碳數4以上且具有羥基之單羧酸之碳數較佳為4～10。作為此種單羧酸，具體而言，可列舉：水楊酸、2-羥基異丁酸、甘油酸、2,2-雙(羥基甲基)丙酸、2,2-雙(羥基甲基)丁酸、羥基三甲基乙酸、蘋果酸等。 作為具有胺基之單羧酸(胺基酸等)，可列舉：丙胺酸、甘胺酸、甘胺醯甘胺酸、胺基丁酸、N-乙醯基甘胺酸、N-(第三丁氧基羰基)甘胺酸、脯胺酸、反式-4-羥基-L-脯胺酸、苯丙胺酸、肌胺酸、乙內醯脲酸、肌酸、肌酸水合物、N-[三(羥基甲基)甲基]甘胺酸等。 其等之中，作為進而較佳之單羧酸，可列舉：四氫呋喃-2-羧酸、2-呋喃甲酸、2-吡啶羧酸、焦麩胺酸、N-[三(羥甲基)甲基]甘胺酸、N-乙醯基甘胺酸、N-(第三丁氧基羰基)甘胺酸、肌酸水合物、2-羥基異丁酸、甘油酸、2,2-雙(羥甲基)丙酸、2,2-雙(羥甲基)丁酸。 其等之中，尤佳之單羧酸係四氫呋喃-2-羧酸、焦麩胺酸、N-乙醯基甘胺酸、2-羥基異丁酸、2,2-雙(羥甲基)丙酸、及2,2-雙(羥甲基)丁酸。 上述單羧酸之中，於在特定之pH值之範圍內與金屬氧化物粒子及非離子性聚合物(P)一併使用之情形時，就維持對氧化矽膜之充分高之研磨速度，並且將對氮化矽膜之研磨速度抑制為較低，而獲得氧化矽膜與氮化矽膜之高選擇比之觀點而言，較佳為具有僅含有氧原子作為雜原子之雜環之單羧酸，尤佳為四氫呋喃-2-羧酸。具有單牙配位基之有機酸可單獨使用1種，亦可併用2種以上。 上述單羧酸所代表之具有單牙配位基之有機酸亦可以鹽之形式使用。作為鹽，可列舉：銨鹽、四級銨鹽、如鉀鹽之鹼金屬鹽、有機胺鹽等。 具有單牙配位基之有機酸之含有比率(濃度)相對於研磨劑之總質量，較佳為0.003質量%以上且1.0質量%以下。於具有單牙配位基之有機酸之含有比率為上述範圍之情形時，充分獲得氧化矽膜之研磨速度提高及選擇比提高之效果，且作為研磨粒之金屬氧化物粒子之分散穩定性亦良好。具有單牙配位基之有機酸之含有比率相對於研磨劑之總質量，較佳為0.003質量%以上且1.0質量%以下，更佳為0.04質量%以上且0.80質量%以下。 (非離子性聚合物(P)) 本發明之研磨劑所含有之非離子性聚合物(P)包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。非離子性聚合物(P)可僅包含其等之1種，亦可包含2種以上。 聚甘油係2個以上之甘油進行聚合而得之甘油之多聚體。聚氧乙烯聚甘油醚係使氧化乙烯與聚甘油加成聚合而獲得之化合物，聚氧丙烯聚甘油醚係使氧化丙烯與聚甘油加成聚合而獲得之化合物。成為聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚之起始物質之聚甘油之聚合度並無特別限定，較佳為2～10，尤佳為2。即，作為聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚，分別較佳為聚氧乙烯二甘油醚及聚氧丙烯二甘油醚。 非離子性聚合物(P)之重量平均分子量較佳為300～10萬，更佳為300～10000。若重量平均分子量為300以上，則可穩定地確保具有單牙配位基之有機酸吸附在金屬氧化物粒子之表面及包含氧化矽膜之被研磨面上之狀態。若重量平均分子量為10萬以下，則於操作性之方面上有利。 非離子性聚合物(P)之中，作為聚甘油，較佳為下述式(1)所表示之聚合物(以下，稱為聚合物(1))。作為聚氧乙烯聚甘油醚，較佳為下述式(2)所表示之聚合物(以下，稱為聚合物(2))。作為聚氧丙烯聚甘油醚，較佳為下述式(3)所表示之聚合物(以下，稱為聚合物(3))。非離子性聚合物(P)可包含選自聚合物(1)、聚合物(2)及聚合物(3)中之1種，亦可包含2種以上。 [化1](其中，於式(1)中，n≧4；於式(2)中，p1＋q1＋r1＋s1≧4；於式(3)中，p2＋q2＋r2＋s2≧4)。 於以下例示聚合物(1)～聚合物(3)之較佳態樣，但非離子性聚合物(P)並不限定於該等。 聚合物(1)係n所示之聚合度為4以上之聚甘油。作為聚合物(1)，較佳為重量平均分子量為300以上之聚甘油。若重量平均分子量為300以上，則可穩定地確保具有單牙配位基之有機酸吸附在金屬氧化物粒子之表面及包含氧化矽膜之被研磨面上之狀態。就操作性等觀點而言，聚合物(1)之重量平均分子量之上限較佳為10萬左右。聚合物(1)之重量平均分子量更佳為300～10000。 再者，式(1)中之n表示分子間之平均之值。n平均為4以上，n之上限係賦予上述上限之重量平均分子量之數值。再者，關於本說明書中之重量平均分子量，只要無特別說明，則係藉由凝膠滲透層析法(GPC)所測定之重量平均分子量。 聚合物(2)係使氧化乙烯與二甘油加成聚合而獲得之聚氧乙烯二甘油醚。作為聚合物(2)，較佳為重量平均分子量為300以上者。若重量平均分子量為300以上，則可穩定地確保具有單牙配位基之有機酸吸附在金屬氧化物粒子之表面及包含氧化矽膜之被研磨面上之狀態。就操作性等觀點而言，聚合物(2)之重量平均分子量之上限較佳為10萬左右。聚合物(2)之重量平均分子量更佳為300～10000。 於式(2)中，4個氧化乙烯鏈之重複單元之合計即p1＋q1＋r1＋s1為4以上，若該合計為4以上，則p1、q1、r1、s1之各個數值並無限定。此處，所謂p1＋q1＋r1＋s1≧4，係表示作為分子間之平均之值之p1＋q1＋r1＋s1為4以上。又，p1＋q1＋r1＋s1之上限係賦予上述上限之重量平均分子量之數值。 聚合物(3)係使氧化丙烯與二甘油加成聚合而獲得之聚氧丙烯二甘油醚。作為聚合物(3)，較佳為重量平均分子量為400以上者。若重量平均分子量為400以上，則可穩定地確保具有單牙配位基之有機酸吸附在金屬氧化物粒子之表面及包含氧化矽膜之被研磨面上之狀態。就操作性等觀點而言，聚合物(3)之重量平均分子量之上限較佳為10萬左右。聚合物(3)之重量平均分子量更佳為400～10000。 於式(3)中，4個氧化丙烯鏈之重複單元之合計即p2＋q2＋r2＋s2為4以上，若該合計為4以上，則p2、q2、r2、s2之各個數值並無限定。此處，所謂p2＋q2＋r2＋s2≧4，係表示作為分子間之平均之值之p2＋q2＋r2＋s2為4以上。又，p2＋q2＋r2＋s2之上限係賦予上述上限之重量平均分子量之數值。 作為聚合物(1)～聚合物(3)之市售品，例如關於聚合物(1)，可列舉：阪本藥品工業股份有限公司製造之聚甘油＃310、聚甘油＃500、聚甘油＃750等。關於聚合物(2)，可列舉：作為「SC-E Series」(商品名，阪本藥品工業股份有限公司製造)之p1＋q1＋r1＋s1為13～40且重量平均分子量為750～2000之聚氧乙烯二甘油醚等。關於聚合物(3)，可列舉：作為「SC-P Series」(商品名，阪本藥品工業股份有限公司製造)之p2＋q2＋r2＋s2為9～24且重量平均分子量為750～1600之聚氧丙烯二甘油醚等。 非離子性聚合物(P)可僅包含選自聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚中之至少1種，尤其是選自聚合物(1)、聚合物(2)及聚合物(3)中之至少1種，亦可於無損本發明之效果之範圍內包含非離子性聚合物(P)以外之非離子性聚合物。非離子性聚合物(P)較佳為僅由選自聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚中之至少1種、尤其是選自聚合物(1)、聚合物(2)及聚合物(3)中之至少1種所構成。 非離子性聚合物(P)之含有比率(濃度)相對於研磨劑之總質量，較佳為0.0002質量%以上且2.0質量%以下。於非離子性聚合物(P)之含量為0.0002質量%以上且2.0質量%以下之情形時，獲得對氧化矽膜充分高之研磨速度，並且獲得高選擇比，且圖案上之平坦性亦良好。非離子性聚合物(P)之含有比率相對於研磨劑之總質量，較佳為0.0005質量%以上且1.0質量%以下，更佳為0.001質量%以上且0.80質量%以下。 (pH值) 本發明之研磨劑之pH值係3.0以上且7.0以下。於研磨劑之pH值為3.0以上且7.0以下之情形時，充分獲得氧化矽膜之研磨速度提高之效果，且作為研磨粒之金屬氧化物粒子之分散穩定性亦良好。研磨劑之pH值更佳為3.0以上且5.0以下，尤佳為3.0以上且4.5以下。 於本發明之研磨劑中，為了使pH值為3.0以上且7.0以下之特定值，亦可含有各種無機酸或無機酸鹽或者鹼性化合物作為pH值調整劑。作為無機酸或無機酸鹽，並無特別限定，例如可使用硝酸、硫酸、鹽酸、磷酸、及其等之銨鹽或者鉀鹽等。鹼性化合物較佳為水溶性，並無特別限定。作為鹼性化合物，例如可使用氨、氫氧化鉀、氫氧化四甲基銨(以下，稱為TMAH)或氫氧化四乙基銨等四級銨氫氧化物、單乙醇胺、乙二胺等有機胺等。 於本發明之研磨劑中，除上述成分以外，亦可含有分散劑(或防凝集劑)。所謂分散劑，係為了使氧化鈰粒子等金屬氧化物粒子穩定地分散於純水等分散介質中而含有者。作為分散劑，可列舉陰離子性、陽離子性、兩性之界面活性劑，或陰離子性、陽離子性、兩性之高分子化合物，可含有其等之1種或2種以上。又，於本發明之研磨劑中，可視需要適當地含有潤滑劑、黏性賦予劑或黏度調節劑、防腐劑等。 關於本發明之研磨劑，為了保管或輸送之便利性，亦可以金屬氧化物粒子之分散液(以下，亦稱為分散液α)、與使具有單牙配位基之有機酸與非離子性聚合物(P)溶解於水中而成之水溶液(以下，亦稱為水溶液β)之兩種液體的形式，且較佳為以兩種液體之pH值均成為3.0以上且7.0以下之方式分別進行準備，並於使用時進行混合。再者，該水溶液β係以下所示之研磨用添加液。 ＜研磨用添加液＞ 本發明之研磨用添加液之特徵在於：其係用以與金屬氧化物粒子之分散液(上述之分散液α)進行混合而製備研磨劑之添加液，該添加液含有具有單牙配位基之有機酸；包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種之非離子性聚合物(上述之非離子性聚合物(P))；及水，且pH值為3.0以上且7.0以下。於研磨劑之製備中，藉由使用該研磨用添加液，可提高研磨劑之保管或輸送之便利性。 於本發明之研磨用添加液中，關於所含有之具有單牙配位基之有機酸、非離子性聚合物(P)、水之各成分，及液體之pH值，係與關於上述研磨劑所含有之各成分及液體之pH值所記載者相同。 於本發明之研磨用添加液中，具有單牙配位基之有機酸之含有比率(濃度)並無特別限定，就添加液之操作容易性、或與金屬氧化物粒子之分散液之混合容易性之觀點而言，較佳為相對於添加液之總量為0.003質量%以上且10質量%以下。 於本發明之研磨用添加液中，非離子性聚合物(P)之含有比率(濃度)並無特別限定，就添加液之操作容易性、或與金屬氧化物粒子之分散液之混合容易性之觀點而言，較佳為相對於添加液之總量為0.0002質量%以上且10質量%以下。 關於本發明之研磨用添加液之pH值，係pH值為3.0以上且7.0以下。於研磨用添加液之pH值為3.0以上且7.0以下之情形時，藉由與金屬氧化物粒子之分散液進行混合，而獲得充分獲得了氧化矽膜之研磨速度提高、及圖案基板之研磨中之平坦性提高等效果，且作為研磨粒之金屬氧化物粒子之分散穩定性亦良好之研磨劑。研磨用添加液之pH值更佳為3.0以上且5.0以下，尤佳為3.0以上且4.5以下。 於與此種研磨用添加液混合之金屬氧化物粒子之分散液中，液體中之金屬氧化物粒子之含有比率(濃度)就金屬氧化物粒子之分散性及分散液之操作容易性等觀點而言，較佳為0.01質量%以上且40質量%以下。更佳為0.01質量%以上且20質量%以下，尤佳為0.01質量%以上且10質量%以下。 藉由將本發明之研磨用添加液與金屬氧化物粒子之分散液進行混合，可實現維持了對氧化矽膜之充分高之平坦性，並且提高了研磨速度之上述研磨劑。再者，於研磨用添加液與金屬氧化物粒子之分散液之混合中，可將研磨用添加液添加至金屬氧化物粒子之分散液中而進行混合，亦可於研磨用添加液中添加金屬氧化物粒子之分散液而進行混合。 研磨用添加液與金屬氧化物粒子之分散液之混合比率並無特別限定，較佳為於混合後之研磨劑中，具有單牙配位基之有機酸及非離子性聚合物(P)之含有比率(濃度)相對於研磨劑之總量分別成為0.003質量%以上且1.0質量%以下及0.0002質量%以上且2.0質量%以下之混合比率。就研磨用添加液及金屬氧化物粒子之分散液之混合容易性之觀點而言，較佳為以研磨用添加液：金屬氧化物粒子之分散液＝130：1～1：130之質量比率進行混合。 再者，於分為金屬氧化物粒子之分散液(分散液α)與本發明之研磨用添加液(水溶液β)之兩種液體，將其等進行混合而製備研磨劑之情形時，可將分散液α中之金屬氧化物粒子之含有比率(濃度)、及研磨用添加液(水溶液β)中之具有單牙配位基之有機酸及非離子性聚合物(P)之各濃度濃縮至用作研磨劑時之2倍～100倍之濃度以進行製備，將經濃縮之兩種液體混合後，於用作研磨劑時進行稀釋而設為特定之濃度。更具體而言，例如於將分散液α中之金屬氧化物粒子之濃度、與研磨用添加液中之具有單牙配位基之有機酸及非離子性聚合物(P)之各濃度均濃縮至10倍而進行製備之情形時，可以10質量份之分散液α、10質量份之研磨用添加液、80質量份之水之比率進行混合，稀釋至10倍而製成研磨劑。 ＜研磨劑之製備方法＞ 為了製備本發明之研磨劑，而使用如下方法：於使上述金屬氧化物粒子分散於純水或離子交換水等水中而成之分散液中加入具有單牙配位基之有機酸、及非離子性聚合物(P)並進行混合。再者，只要僅利用上述成分且以pH值成為上述特定範圍內之方式能夠製備研磨劑即可，但於pH值不處在上述特定範圍內之情形時，進而加入pH值調整劑，以所獲得之研磨劑之pH值成為上述特定範圍內之方式進行製備。混合後，使用攪拌機等攪拌特定時間，藉此獲得均一之研磨劑。又，混合後，亦可使用超音波分散機而獲得更良好之分散狀態。 本發明之研磨劑未必必須以預先構成之將研磨成分全部混合而成者之形式供給於研磨場所。於供給於研磨場所時，亦可將研磨成分混合而成為研磨劑之組成。 為了保管或輸送之便利性，本發明之研磨劑亦可以金屬氧化物粒子之分散液(分散液α)、與上述研磨用添加液(水溶液β)之兩種液體之形式分別進行準備，並於使用時混合。於分為分散液α與水溶液β之兩種液體，將其等進行混合而製備研磨劑之情形時，如上所述，亦可預先將水溶液β中之具有單牙配位基之有機酸及非離子性聚合物(P)之濃度濃縮至研磨劑使用時之例如10倍左右，混合後以成為特定濃度之方式利用水進行稀釋，之後使用。 ＜研磨方法＞ 本發明之實施形態之研磨方法係一面供給上述研磨劑一面使研磨對象物之被研磨面與研磨墊接觸，藉由兩者之相對運動而進行研磨之方法。此處，供進行研磨之被研磨面例如為半導體基板之含有包含二氧化矽之面之表面。作為半導體基板，可列舉上述STI用之基板作為較佳例。本發明之研磨方法於半導體元件之製造中，對用以多層配線間之層間絕緣膜之平坦化之研磨亦有效。 作為STI用基板中之二氧化矽膜，可列舉：以四乙氧基矽烷(TEOS)為原料並利用電漿CVD(Chemical Vapor Deposition，化學氣相沈積)法所成膜之所謂PE-TEOS(Plasma Enhanced-TEOS，電漿增強-四乙氧基矽烷)膜。又，作為二氧化矽膜，亦可列舉：利用高密度電漿CVD法所成膜之所謂HDP(High Density Plasma)膜。作為氮化矽膜，可列舉：以矽烷或二氯矽烷與氨為原料並利用低壓CVD法或電漿CVD法所成膜者。 藉由使用本發明之研磨劑並利用上述方法進行研磨，可實現高平坦化。平坦性之評價係例如使用STI用之圖案晶圓進行。STI用之圖案之研磨較理想為於氮化矽膜露出之時點停止，圖案晶圓之氮化矽膜越不會被削減，對平坦性越有利。因此，可將氮化矽膜之膜厚之減少量設為平坦性之指標。氮化矽膜之膜厚減少量越少，則意指平坦性越好。 於本發明之實施形態之研磨方法中，可使用公知之研磨裝置。圖2係表示可用於本發明之研磨方法之研磨裝置之一例之圖。 該研磨裝置20具備：保持如STI基板之半導體基板21之研磨頭22、研磨壓盤23、貼附於研磨壓盤23之表面之研磨墊24、及將研磨劑25向研磨墊24進行供給之研磨劑供給配管26。其以如下方式構成：一面自研磨劑供給配管26供給研磨劑25，一面使由研磨頭22保持之半導體基板21之被研磨面與研磨墊24接觸，使研磨頭22與研磨壓盤23進行相對旋轉運動而進行研磨。再者，用於本發明之實施形態之研磨裝置並不限定於此種構造者。 研磨頭22不僅可進行旋轉運動，亦可進行直線運動。又，研磨壓盤23及研磨墊24亦可為與半導體基板21相同程度之尺寸或小於其之尺寸。於該情形時，較佳為使研磨頭22與研磨壓盤23相對移動，藉此可對半導體基板21之被研磨面之整個面進行研磨。進而，研磨壓盤23及研磨墊24亦可不進行旋轉運動，例如可以傳送帶方式單向地移動。 此種研磨裝置20之研磨條件並無特別限制，可藉由對研磨頭22施加負荷並將之壓抵於研磨墊24，而進一步提高研磨壓力，使研磨速度提高。研磨壓力較佳為0.5～50 kPa左右，就研磨速度下之半導體基板21之被研磨面內之均勻性、平坦性、防止刮痕等研磨缺陷之觀點而言，研磨壓力更佳為3～40 kPa左右。研磨壓盤23及研磨頭22之轉數較佳為50～500 rpm左右，但並不限定於此。又，關於研磨劑25之供給量，係根據研磨劑之組成或上述各研磨條件等而適當調整。 作為研磨墊24，可使用包含不織布、發泡聚胺基甲酸酯、多孔質樹脂、非多孔質樹脂等者。為了促進研磨劑25向研磨墊24之供給，或者於研磨墊24積存一定量之研磨劑25，亦可對研磨墊24之表面實施格子狀、同心圓狀、螺旋狀等之溝槽加工。又，亦可視需要使墊調整器與研磨墊24之表面接觸，一面對研磨墊24表面進行調整一面進行研磨。 根據本發明之研磨方法，於半導體元件之製造中之層間絕緣膜之平坦化或STI用絕緣膜之平坦化等之CMP處理中，可以較高之研磨速度對包含氧化矽(例如二氧化矽)之被研磨面進行研磨，並且可實現氧化矽膜與氮化矽膜之高選擇比，而達成較高之平坦性。 [實施例] 以下，藉由實施例及比較例對本發明具體地進行說明，但本發明並不限定於該等實施例。 例1～15係實施例，例16～20係比較例。於以下之例中，只要無特別說明，則「%」意指質量%。又，特性值係藉由下述方法進行測定並評價。 [pH值] pH值係使用東亞DKK公司製造之pH值計HM-30R而測得。 [平均二次粒徑] 平均二次粒徑係使用雷射散射/繞射式粒度分佈測定裝置(堀場製作所製造，裝置名：LA-920)而測得。 [研磨特性] 研磨特性係使用全自動CMP研磨裝置(Applied Materials公司製造，裝置名：Mirra)進行以下之研磨並進行評價。研磨墊係使用雙層墊(Dow公司製造之VP-3100)，且於研磨墊之調整時使用CVD金剛石墊調整器(3M公司製造，商品名：Trizact B5)。研磨條件係將研磨壓力設為21 kPa，將研磨壓盤之轉數設為77 rpm，將研磨頭之轉數設為73 rpm。又，研磨劑之供給速度係設為200毫升/分鐘。 為了測定研磨速度，分別使用以四乙氧基矽烷為原料並藉由電漿CVD於8英吋矽晶圓上成膜二氧化矽膜所得之附二氧化矽膜之毯覆式基板，與藉由CVD於8英吋矽晶圓上成膜氮化矽膜所得之附氮化矽膜之毯覆式基板作為研磨對象物(被研磨物)。 成膜於毯覆式基板上之二氧化矽膜與氮化矽膜之膜厚之測定係使用KLA-Tencor公司之膜厚計UV-1280SE。藉由求出毯覆式基板之研磨前之膜厚與研磨1分鐘後之膜厚的差，而分別算出二氧化矽膜與氮化矽膜之研磨速度。將自基板之面內49處之研磨速度獲得之研磨速度的平均值(Å/分鐘)設為研磨速度之評價指標。又，算出二氧化矽膜之研磨速度與氮化矽膜之研磨速度之比(二氧化矽膜之研磨速度/氮化矽膜之研磨速度)作為選擇比。 [例1] 將使平均二次粒徑120 nm之氧化鈰粒子分散於純水中所得之氧化鈰分散液(以下，稱為氧化鈰分散液a)以氧化鈰粒子相對於研磨劑之總質量之含有比率(濃度)成為0.25%之方式加入至純水中後，進而分別將作為具有單牙配位基之有機酸之四氫呋喃-2-羧酸(以下，稱為「THF-C」)以含有比率(濃度)成為0.10%之方式加入，將作為聚合物(2)之聚氧乙烯二甘油醚(商品名：SC-E750，阪本藥品工業股份有限公司製造，式(2)中之p1＋q1＋r1＋s1≒13，重量平均分子量：750)(以下，稱為非離子性聚合物A。於表1中，表示為「聚氧乙烯二甘油醚(Mw750)」。Mw意指重量平均分子量)以含有比率(濃度)成為0.010%之方式加入，並進行攪拌，進而加入單乙醇胺(以下，表示為MEA)，將pH值調整為3.5，而獲得研磨劑(1)。 [例2～9] 與例1同樣地，將氧化鈰分散液a、四氫呋喃-2-羧酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(2)～(9)。 [例10] 與例1同樣地，將氧化鈰分散液a、四氫呋喃-2-羧酸及作為聚合物(1)之聚甘油(商品名：聚甘油＃310，阪本藥品工業股份有限公司製造，重量平均分子量：310)(以下，稱為非離子性聚合物B。於表1中，表示為「聚甘油(Mw310)」)分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(10)。 [例11] 與例1同樣地，將氧化鈰分散液a、四氫呋喃-2-羧酸及作為聚合物(3)之聚氧丙烯二甘油醚(商品名：SC-P400，阪本藥品工業股份有限公司製造，式(3)中之p2＋q2＋r2＋s2≒4，重量平均分子量：400)(以下，稱為非離子性聚合物C。於表1中，表示為「聚氧丙烯二甘油醚(Mw400)」)分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(11)。 [例12] 將使平均二次粒徑100 nm之氧化鈰粒子分散於純水中所得之氧化鈰分散液(以下，稱為氧化鈰分散液b)以氧化鈰粒子相對於研磨劑之總質量之含有比率(濃度)成為0.25%之方式加入至純水中後，將四氫呋喃-2-羧酸與作為聚合物(2)之聚氧乙烯二甘油醚(商品名：SC-E1000，阪本藥品工業股份有限公司製造，式(2)中之p1＋q1＋r1＋s1≒20，重量平均分子量：1000)(以下稱為非離子性聚合物D。於表1中，表示為「聚氧乙烯二甘油醚(Mw1000)」)分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(12)。 [例13] 與例1同樣地，將氧化鈰分散液a、作為具有單牙配位基之有機酸之N-乙醯基甘胺酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(13)。 [例14] 將使平均二次粒徑170 nm之氧化鈰粒子分散於純水中所得之氧化鈰分散液(以下，稱為氧化鈰分散液c)以氧化鈰粒子相對於研磨劑之總質量之含有比率(濃度)成為0.25%之方式加入至純水中後，將作為具有單牙配位基之有機酸之2,2-雙(羥基甲基)丙酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(14)。 [例15] 與例14同樣地，將氧化鈰分散液c、作為具有單牙配位基之有機酸之DL-焦麩胺酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(15)。 [例16] 與例1同樣地，將氧化鈰分散液a、四氫呋喃-2-羧酸及聚乙烯醇(並非非離子性聚合物(P)之非離子性聚合物)分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(16)。 [例17] 與例14同樣地，將氧化鈰分散液c及DL-焦麩胺酸分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(17)。 [例18] 與例1同樣地，將氧化鈰分散液a及四氫呋喃-2-羧酸以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值，而獲得研磨劑(18)。 [例19] 與例1同樣地，將氧化鈰分散液a、四氫呋喃-2-羧酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入MEA，調整為表1所示之pH值(本發明之研磨劑之範圍外之pH值)，而獲得研磨劑(19)。 [例20] 與例1同樣地，將氧化鈰分散液a、作為並非具有單牙配位基之有機酸之有機酸的聚丙烯酸及非離子性聚合物A分別以成為表1所示之含有比率(濃度)之方式加入至純水中並進行攪拌，進而加入硝酸，調整為表1所示之pH值，而獲得研磨劑(20)。 分別利用上述方法對例1～20中所獲得之研磨劑(1)～(20)之研磨特性(二氧化矽膜之研磨速度、氮化矽膜之研磨速度、及選擇比)進行測定。將測定結果示於表1。 [表1] 根據表1可知下述情況。即，藉由使用含有作為金屬氧化物粒子之氧化鈰粒子、具有單牙配位基之有機酸、非離子性聚合物(P)、及水，且pH值為3.0以上且7.0以下之例1～15之研磨劑(1)～(15)進行研磨，而獲得對二氧化矽膜之較高之研磨速度。又，可知二氧化矽膜與氮化矽膜之選擇比變得極高。 相對於此，可知於使用含有聚乙烯醇作為非離子性聚合物但不含有非離子性聚合物(P)之例16之研磨劑(16)，及完全不含有非離子性聚合物之例17之研磨劑(17)之情形時，二氧化矽膜之研磨速度與例1～15相比大幅度地變低。又，可知於使用完全不含有非離子性聚合物，且具有單牙配位基之有機酸之種類與例17不同之例18之研磨劑(18)、含有並非具有單牙配位基之有機酸之有機酸即聚丙烯酸之例20之研磨劑(20)的情形時，二氧化矽膜與氮化矽膜之選擇比與例1～15相比大幅度地變低。又，於使用將pH值調整至8.5之例19之研磨劑(19)之情形時，由於產生凝集故而無法評價研磨速度。 本申請案係基於2016年9月13日提出申請之日本專利申請2016-178507者，且其內容係作為參照併入本文中。 [產業上之可利用性] 根據本發明，例如於含有包含氧化矽之面之被研磨面之CMP中，可維持對氧化矽膜之充分高之研磨速度，並且將氮化矽膜之研磨速度抑制為較低，而達成氧化矽膜與氮化矽膜之高選擇比。因此，本發明之研磨劑及研磨方法對於半導體元件製造中之STI用絕緣膜之平坦化較佳。Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments, as long as it conforms to the gist of the present invention, other embodiments may also belong to the scope of the present invention. <Abrasive> The abrasive of the present invention is characterized in that it contains metal oxide particles, an organic acid having a single-dentate ligand, a nonionic polymer, and water, and has a pH value of 3.0 or more and 7.0 or less The non-ionic polymer includes at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether. Hereinafter, a nonionic polymer including at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether is also referred to as a nonionic polymer (P). In the case where the polishing agent of the present invention is used for CMP of a polished surface including a silicon oxide film (such as a silicon dioxide film) in an STI, the polishing speed of the silicon oxide film is high, and The polishing speed of the film is sufficiently low, and a high selection ratio of the silicon oxide film and the silicon nitride film can be achieved. In addition, polishing with high flatness can be achieved. The mechanism by which the abrasive of the present invention exhibits excellent abrasive properties as described above has not been clarified, but it is believed that the reason is that the abrasive contains an organic acid having a single-dentate ligand and a nonionic polymer (P) having a specific molecular structure. Both. That is, the reason is considered to be that the organic acid having a single-dentate ligand contained in the abrasive has a pH value of 3.0 or more and 7.0 or less in the presence of the above-mentioned non-ionic polymer (P) having a specific molecular structure. In the region, the end surface of the molecule is electrostatically adsorbed on the surface of the metal oxide particles and the polished surface including the silicon oxide film. In addition, it is considered that as a result of optimizing the state of the surface of the metal oxide particles and the surface of the polished surface including the silicon oxide film, the dispersion of the metal oxide particles is not impaired, and a higher level of the silicon oxide film is obtained. Both the polishing speed and the high selection ratio of the silicon oxide film and the silicon nitride film. Hereinafter, each component contained in the abrasive | polishing agent of this invention, and pH value are demonstrated. (Metal oxide particles) The metal oxide particles contained in the abrasive of the present invention have a function as abrasive particles. Examples of the metal oxide particles include particles of a metal oxide such as cerium oxide, aluminum oxide, silicon dioxide, titanium oxide, and zirconia. The metal oxide particles are preferably cerium oxide particles in terms of the polishing rate of the silicon oxide film. When the cerium oxide particles are used as the metal oxide particles in the abrasive of the present invention, the cerium oxide particles contained in the abrasive are not particularly limited. For example, Japanese Patent Application Laid-Open No. 11-12561 or Japan Cerium oxide particles produced by a method described in Japanese Patent Laid-Open No. 2001-35818. That is, cerium oxide particles can be produced by adding a base to an aqueous solution of cerium (IV) ammonium nitrate to prepare a cerium hydroxide gel, and filtering, washing, and firing the cerium oxide particles, or high-purity cerium oxide particles. It is obtained by pulverizing cerium carbonate and calcining, and then pulverizing and classifying. Further, cerium oxide particles may be used which are obtained by chemically oxidizing a cerium (III) salt in a liquid as described in Japanese Patent Application Publication No. 2010-505735. The average particle diameter of the metal oxide particles is preferably from 10 nm to 500 nm, and more preferably from 30 nm to 300 nm. If the average particle diameter exceeds 500 nm, there is a possibility that polishing damage such as scratches may occur on the surface to be polished. In addition, if the average particle diameter is less than 10 nm, not only may the polishing speed be reduced, but also the surface area ratio per unit volume is large, so it is easily affected by the surface state, and according to conditions such as pH value or concentration of additives On the other hand, the metal oxide particles become easily aggregated. For example, the metal oxide particles of cerium oxide particles exist in the form of aggregated particles (secondary particles) formed by aggregating primary particles in the abrasive. Therefore, the preferred particle size of the metal oxide particles is set as an average secondary particle. Trail signifier. That is, the metal oxide particles preferably have an average secondary particle diameter of 10 nm to 500 nm, and more preferably 30 nm to 300 nm. The average secondary particle diameter is measured using a dispersion liquid dispersed in a dispersion medium such as pure water, and a particle size distribution meter such as laser diffraction or scattering type. The content ratio (concentration) of the metal oxide particles is preferably 0.01% by mass or more and 10% by mass or less with respect to the total mass of the abrasive. When the content ratio of the metal oxide particles is 0.01 mass% or more and 10 mass% or less, a sufficiently high polishing rate for the silicon oxide film is obtained. In addition, the viscosity of the abrasive is not too high and the operation is good. The content ratio (concentration) of the metal oxide particles is more preferably from 0.025 mass% to 3.0 mass%, and even more preferably from 0.025 mass% to 1.0 mass%. The metal oxide particles may be used in a state dispersed in a medium in advance (hereinafter referred to as a metal oxide particle dispersion). As the medium, water can be preferably used. (Water) The abrasive of the present invention contains water as a medium for dispersing the metal oxide particles and as a medium for dissolving the organic acid and nonionic polymer (P) having a monodentate ligand described below. There is no particular limitation on the type of water, but considering the effect on organic acids and nonionic polymers (P) with monodentate ligands, the prevention of impurities, and the effect on pH, it is preferable to use pure Water, ultrapure water, ion-exchanged water, etc. (Organic acid having a monodentate ligand) As the organic acid having a monodentate ligand contained in the abrasive of the present invention, a monocarboxylic acid is preferred. The monocarboxylic acid is preferably at least one selected from a monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having 4 or more carbon atoms and a hydroxyl group, and a monocarboxylic acid having an amine group. The monocarboxylic acids which can be preferably used in the abrasive of the present invention are listed below, but are not limited thereto. As the monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having a heterocyclic ring containing a nitrogen atom (nitrogen-containing heterocyclic ring) or a monocarboxylic acid having a heterocyclic ring containing a heteroatom other than nitrogen can be preferably used. Examples of the monocarboxylic acid having a nitrogen atom-containing heterocyclic ring (nitrogen-containing heterocyclic ring) include 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, pyridinecarboxylic acid, and 2-quinolinecarboxylic acid. (Quinolinic acid), pyrrolidone carboxylic acid, DL-pyroglutamic acid, DL-2-piperidinecarboxylic acid, and the like. Examples of the monocarboxylic acid having a heterocyclic ring containing a hetero atom other than nitrogen include a monocarboxylic acid having a heterocyclic ring containing only an oxygen atom as a hetero atom, and specifically, 2-furancarboxylic acid, 3-furancarboxylic acid, Tetrahydrofuran-2-carboxylic acid and the like. The number of carbons of the monocarboxylic acid having 4 or more carbon atoms and having a hydroxyl group is preferably 4 to 10. Specific examples of such a monocarboxylic acid include salicylic acid, 2-hydroxyisobutyric acid, glyceric acid, 2,2-bis (hydroxymethyl) propionic acid, and 2,2-bis (hydroxymethyl) ) Butyric acid, hydroxytrimethylacetic acid, malic acid and the like. Examples of the monocarboxylic acid (amino acid, etc.) having an amino group include alanine, glycine, glycine / glycine, aminobutyric acid, N-acetamidoglycine, N- ( Tributoxycarbonyl) glycine, proline, trans-4-hydroxy-L-proline, phenylalanine, sarcosine, hydantoin, creatine, creatine hydrate, N- [Tris (hydroxymethyl) methyl] glycine and the like. Among these, as further preferable monocarboxylic acids, tetrahydrofuran-2-carboxylic acid, 2-furancarboxylic acid, 2-pyridinecarboxylic acid, pyroglutamic acid, and N- [tris (hydroxymethyl) methyl group are mentioned. ] Glycine, N-Ethyl Glycine, N- (Third Butoxycarbonyl) Glycine, Creatine Hydrate, 2-Hydroxyisobutyric Acid, Glyceric Acid, 2,2-Bis (hydroxy Methyl) propanoic acid, 2,2-bis (hydroxymethyl) butanoic acid. Among them, particularly preferred monocarboxylic acids are tetrahydrofuran-2-carboxylic acid, pyroglutamic acid, N-acetamylglycine, 2-hydroxyisobutyric acid, and 2,2-bis (hydroxymethyl). Propionic acid and 2,2-bis (hydroxymethyl) butanoic acid. Among the above monocarboxylic acids, when the metal oxide particles and the nonionic polymer (P) are used together in a specific pH range, a sufficiently high polishing rate for the silicon oxide film is maintained. In addition, from the viewpoint of suppressing the polishing rate of the silicon nitride film to a low value and obtaining a high selection ratio of the silicon oxide film and the silicon nitride film, it is preferable to have a heterocyclic ring containing only an oxygen atom as a hetero atom. A carboxylic acid, particularly preferably tetrahydrofuran-2-carboxylic acid. The organic acid having a monodentate ligand may be used singly or in combination of two or more kinds. The organic acid having a monodentate ligand represented by the aforementioned monocarboxylic acid may also be used in the form of a salt. Examples of the salt include ammonium salts, quaternary ammonium salts, alkali metal salts such as potassium salts, and organic amine salts. The content ratio (concentration) of the organic acid having a monodentate ligand is preferably 0.003 mass% or more and 1.0 mass% or less with respect to the total mass of the abrasive. When the content ratio of the organic acid having a single-dentate ligand is in the above range, the effects of increasing the polishing speed and the selection ratio of the silicon oxide film are fully obtained, and the dispersion stability of the metal oxide particles as abrasive particles is also improved. good. The content ratio of the organic acid having a monodentate ligand to the total mass of the abrasive is preferably 0.003 mass% or more and 1.0 mass% or less, and more preferably 0.04 mass% or more and 0.80 mass% or less. (Nonionic polymer (P)) The nonionic polymer (P) contained in the abrasive of the present invention is selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether. At least one of them. The nonionic polymer (P) may include only one kind thereof, or may include two or more kinds thereof. Polyglycerol is a polymer of glycerol obtained by polymerizing two or more glycerols. Polyoxyethylene polyglyceryl ether is a compound obtained by addition polymerization of ethylene oxide and polyglycerin, and polyoxypropylene polyglyceryl ether is a compound obtained by addition polymerization of propylene oxide and polyglycerin. The degree of polymerization of the polyglycerol that becomes the starting material of the polyoxyethylene polyglyceryl ether and the polyoxypropylene polyglyceryl ether is not particularly limited, but is preferably 2 to 10, and particularly preferably 2. That is, as a polyoxyethylene polyglyceryl ether and a polyoxypropylene polyglyceryl ether, a polyoxyethylene diglyceryl ether and a polyoxypropylene diglyceryl ether are respectively preferable. The weight-average molecular weight of the nonionic polymer (P) is preferably 300 to 100,000, and more preferably 300 to 10,000. When the weight average molecular weight is 300 or more, the state where the organic acid having a single-dentate ligand is adsorbed on the surface of the metal oxide particles and the polished surface including the silicon oxide film can be stably ensured. When the weight average molecular weight is 100,000 or less, it is advantageous in terms of workability. Among the nonionic polymers (P), the polyglycerin is preferably a polymer represented by the following formula (1) (hereinafter referred to as a polymer (1)). The polyoxyethylene polyglyceryl ether is preferably a polymer represented by the following formula (2) (hereinafter referred to as a polymer (2)). The polyoxypropylene polyglyceryl ether is preferably a polymer represented by the following formula (3) (hereinafter, referred to as a polymer (3)). The nonionic polymer (P) may include one kind selected from the polymer (1), the polymer (2), and the polymer (3), and may include two or more kinds. [Chemical 1] (Wherein n ≧ 4 in formula (1); p1 + q1 + r1 + s1 ≧ 4 in formula (2); p2 + q2 + r2 + s2 ≧ 4 in formula (3)). Preferred examples of the polymer (1) to the polymer (3) are exemplified below, but the nonionic polymer (P) is not limited to these. The polymer (1) is a polyglycerin having a degree of polymerization of 4 or more as shown by n. The polymer (1) is preferably a polyglycerin having a weight average molecular weight of 300 or more. When the weight average molecular weight is 300 or more, the state where the organic acid having a single-dentate ligand is adsorbed on the surface of the metal oxide particles and the polished surface including the silicon oxide film can be stably ensured. From the viewpoints of workability and the like, the upper limit of the weight average molecular weight of the polymer (1) is preferably about 100,000. The weight average molecular weight of the polymer (1) is more preferably 300 to 10,000. In addition, n in Formula (1) represents the average value between molecules. The average n is 4 or more, and the upper limit of n is a numerical value of the weight average molecular weight given to the above upper limit. The weight average molecular weight in this specification is a weight average molecular weight measured by gel permeation chromatography (GPC) unless otherwise specified. The polymer (2) is a polyoxyethylene diglyceryl ether obtained by addition polymerization of ethylene oxide and diglycerin. The polymer (2) is preferably one having a weight average molecular weight of 300 or more. When the weight average molecular weight is 300 or more, the state where the organic acid having a single-dentate ligand is adsorbed on the surface of the metal oxide particles and the polished surface including the silicon oxide film can be stably ensured. From the viewpoint of workability and the like, the upper limit of the weight average molecular weight of the polymer (2) is preferably about 100,000. The weight average molecular weight of the polymer (2) is more preferably 300 to 10,000. In formula (2), the total of the repeating units of the four ethylene oxide chains is p1 + q1 + r1 + s1 is 4 or more. If the total is 4 or more, each value of p1, q1, r1, s1 is not limited. Here, p1 + q1 + r1 + s1 ≧ 4 means that p1 + q1 + r1 + s1, which is an average value between molecules, is 4 or more. The upper limit of p1 + q1 + r1 + s1 is a numerical value of the weight average molecular weight given to the above upper limit. The polymer (3) is a polyoxypropylene diglyceryl ether obtained by addition polymerization of propylene oxide and diglycerin. The polymer (3) is preferably one having a weight average molecular weight of 400 or more. When the weight average molecular weight is 400 or more, the state in which the organic acid having a single-dentate ligand is adsorbed on the surface of the metal oxide particles and the polished surface including the silicon oxide film can be stably ensured. From the viewpoint of workability and the like, the upper limit of the weight average molecular weight of the polymer (3) is preferably about 100,000. The weight average molecular weight of the polymer (3) is more preferably 400 to 10,000. In formula (3), the total of the repeating units of the four propylene oxide chains, that is, p2 + q2 + r2 + s2 is 4 or more. If the total is 4 or more, each value of p2, q2, r2, s2 is not limited. Here, p2 ++ q2 ++ r2 ++ s2 ≧ 4 means that p2 ++ q2 ++ r2 ++ s2, which is an average value between molecules, is 4 or more. The upper limit of p2 + q2 + r2 + s2 is a numerical value of the weight average molecular weight given to the above upper limit. Examples of commercially available polymers (1) to (3) include polymer (1), polyglycerol # 310, polyglycerol # 500, and polyglycerol # 750 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd. Wait. As the polymer (2), a polyoxyethylene diglyceryl ether having a p1 + q1 + r1 + s1 of 13 to 40 and a weight average molecular weight of 750 to 2000 as "SC-E Series" (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd.) Wait. Regarding the polymer (3), a polyoxypropylene diglyceryl ether having a p2 + q2 + r2 ++ s2 of 9 to 24 and a weight average molecular weight of 750 to 1600 as the "SC-P Series" (trade name, manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.) is mentioned. Wait. The nonionic polymer (P) may contain at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether, and is particularly selected from polymer (1), polymer (2) And at least one of the polymer (3), a nonionic polymer other than the nonionic polymer (P) may be contained within a range that does not impair the effect of the present invention. The nonionic polymer (P) is preferably composed of at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether, and is particularly selected from polymer (1), polymer ( 2) and at least one of the polymer (3). The content ratio (concentration) of the nonionic polymer (P) is preferably 0.0002 mass% or more and 2.0 mass% or less with respect to the total mass of the abrasive. When the content of the nonionic polymer (P) is 0.0002% by mass or more and 2.0% by mass or less, a sufficiently high polishing rate for the silicon oxide film is obtained, a high selection ratio is obtained, and the flatness on the pattern is also good. . The content ratio of the nonionic polymer (P) to the total mass of the abrasive is preferably 0.0005 mass% or more and 1.0 mass% or less, and more preferably 0.001 mass% or more and 0.80 mass% or less. (pH) The pH of the abrasive of the present invention is 3.0 or more and 7.0 or less. When the pH of the abrasive is 3.0 or more and 7.0 or less, the effect of improving the polishing rate of the silicon oxide film is sufficiently obtained, and the dispersion stability of the metal oxide particles as the abrasive particles is also good. The pH of the abrasive is more preferably 3.0 or more and 5.0 or less, and even more preferably 3.0 or more and 4.5 or less. The abrasive of the present invention may contain various inorganic acids or inorganic acid salts or basic compounds as a pH adjuster in order to make the pH value to a specific value of 3.0 or more and 7.0 or less. The inorganic acid or the inorganic acid salt is not particularly limited. For example, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and ammonium salts or potassium salts thereof can be used. The basic compound is preferably water-soluble and is not particularly limited. As the basic compound, for example, quaternary ammonium hydroxide such as ammonia, potassium hydroxide, tetramethylammonium hydroxide (hereinafter referred to as TMAH) or tetraethylammonium hydroxide, organics such as monoethanolamine and ethylenediamine can be used. Amine, etc. The abrasive of the present invention may contain a dispersant (or an anti-aggregation agent) in addition to the above-mentioned components. The dispersant is contained in order to stably disperse metal oxide particles such as cerium oxide particles in a dispersion medium such as pure water. Examples of the dispersant include anionic, cationic, and amphoteric surfactants, or anionic, cationic, and amphoteric polymer compounds, and may contain one or two or more of them. In addition, the abrasive of the present invention may appropriately contain a lubricant, a viscosity imparting agent, a viscosity adjusting agent, a preservative, and the like, as necessary. Regarding the abrasive of the present invention, for convenience of storage or transportation, a dispersion liquid of metal oxide particles (hereinafter, also referred to as dispersion liquid α), an organic acid having a single-dentate ligand, and nonionic properties may be used. The polymer (P) is dissolved in water in the form of two liquids of an aqueous solution (hereinafter, also referred to as an aqueous solution β), and is preferably performed separately so that the pH values of the two liquids become 3.0 or more and 7.0 or less. Prepare and mix while using. The aqueous solution β is an additive liquid for polishing as shown below. <Additive liquid for polishing> The additive liquid for polishing of the present invention is characterized in that it is an additive liquid for preparing an abrasive by mixing it with a dispersion liquid of the metal oxide particles (the above-mentioned dispersion liquid α), and the additive liquid contains Organic acid having a single-dentate ligand; a nonionic polymer containing at least one selected from the group consisting of polyglycerol, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether (the above-mentioned nonionic Polymer (P)); and water, and the pH is 3.0 or more and 7.0 or less. In the preparation of the abrasive, the convenience of storage or transportation of the abrasive can be improved by using the polishing additive. In the polishing additive of the present invention, the organic acid, nonionic polymer (P), water, and the pH value of the liquid containing the single-dentate ligand are related to the above-mentioned polishing agent. The pH value of each component and liquid contained is the same. In the grinding additive liquid of the present invention, the content ratio (concentration) of the organic acid having a single-dentate ligand is not particularly limited, and the ease of handling of the additive liquid or the mixing with the dispersion liquid of metal oxide particles is easy. From the viewpoint of performance, it is preferably 0.003% by mass or more and 10% by mass or less with respect to the total amount of the additive liquid. In the grinding additive liquid of the present invention, the content ratio (concentration) of the nonionic polymer (P) is not particularly limited, and the ease of handling of the additive liquid or the ease of mixing with the dispersion liquid of the metal oxide particles is not limited. From a viewpoint, it is preferable that it is 0.0002 mass% or more and 10 mass% or less with respect to the total amount of an addition liquid. Regarding the pH of the polishing additive of the present invention, the pH is 3.0 or more and 7.0 or less. When the pH of the polishing additive solution is 3.0 or more and 7.0 or less, mixing with a dispersion liquid of metal oxide particles can sufficiently improve the polishing speed of the silicon oxide film and the polishing of the pattern substrate. It is an abrasive having good effects such as improvement in flatness and good dispersion stability of metal oxide particles as abrasive particles. The pH of the polishing additive is more preferably 3.0 or more and 5.0 or less, and even more preferably 3.0 or more and 4.5 or less. In a dispersion liquid of metal oxide particles mixed with such a grinding additive liquid, the content ratio (concentration) of the metal oxide particles in the liquid is based on the viewpoint of the dispersibility of the metal oxide particles and the ease of handling the dispersion liquid. In other words, it is preferably 0.01% by mass or more and 40% by mass or less. It is more preferably 0.01% by mass or more and 20% by mass or less, and even more preferably 0.01% by mass or more and 10% by mass or less. By mixing the polishing additive liquid of the present invention with the dispersion liquid of metal oxide particles, the above-mentioned polishing agent which maintains a sufficiently high flatness to the silicon oxide film and improves the polishing speed can be realized. In addition, in the mixing of the polishing additive liquid and the dispersion liquid of the metal oxide particles, the polishing additive liquid may be added to the dispersion liquid of the metal oxide particles and mixed, or the metal may be added to the polishing additive liquid. A dispersion of oxide particles is mixed. The mixing ratio of the grinding additive liquid and the dispersion liquid of the metal oxide particles is not particularly limited, but it is preferably an organic acid having a single tooth ligand and a nonionic polymer (P) in the mixed abrasive. The content ratio (concentration) is a mixing ratio of 0.003 mass% or more and 1.0 mass% or less and 0.0002 mass% or more and 2.0 mass% or less with respect to the total amount of the abrasive. From the viewpoint of the ease of mixing of the polishing additive liquid and the dispersion liquid of the metal oxide particles, it is preferably performed at a mass ratio of the polishing additive liquid: the dispersion liquid of the metal oxide particles = 130: 1 to 1: 130. mixing. In addition, when the two liquids of the dispersion liquid (dispersion liquid α) of the metal oxide particles and the grinding additive liquid (aqueous solution β) of the present invention are mixed, and these are mixed to prepare an abrasive, The concentration ratio (concentration) of the metal oxide particles in the dispersion α and the concentration of the organic acid and the nonionic polymer (P) having a monodentate ligand in the polishing additive (aqueous solution β) are concentrated to When it is used as an abrasive, it is prepared at a concentration of 2 to 100 times, and after concentrating the two liquids, it is diluted to a specific concentration when used as an abrasive. More specifically, for example, the concentration of the metal oxide particles in the dispersion liquid α and the concentrations of the organic acid having a single-dentate ligand and the nonionic polymer (P) in the polishing additive liquid are concentrated. In the case of preparation at 10 times, the abrasive can be prepared by mixing 10 parts by mass of the dispersion liquid α, 10 parts by mass of the grinding additive liquid, and 80 parts by mass of water, and diluting them to 10 times. <Preparation method of the abrasive> In order to prepare the abrasive of the present invention, the following method is used: a single-dentate ligand is added to a dispersion obtained by dispersing the metal oxide particles in water such as pure water or ion-exchanged water; The organic acid and the nonionic polymer (P) are mixed. In addition, as long as the abrasive can be prepared using only the above-mentioned components and the pH value falls within the above-mentioned specific range, when the pH value is not within the above-mentioned specific range, a pH-adjusting agent is further added, so that The obtained abrasive is prepared in such a manner that the pH value falls within the above specific range. After mixing, a homogenous abrasive is obtained by stirring for a specific time using a blender or the like. Also, after mixing, an ultrasonic disperser can be used to obtain a better dispersion state. The abrasive of the present invention does not necessarily need to be supplied to a polishing site in a form that is prepared by mixing all the grinding components in advance. When supplied to a polishing place, the polishing ingredients may be mixed to form a composition of an abrasive. For the convenience of storage or transportation, the abrasive of the present invention may also be prepared separately in the form of two liquids (dispersion liquid α) of the metal oxide particles and the above-mentioned polishing additive liquid (aqueous solution β). Mix while using. In the case where the dispersion liquid α and the aqueous solution β are divided into two liquids and mixed to prepare an abrasive, as described above, the organic acid and non-organic acid having a single-dentate ligand in the aqueous solution β may be previously prepared. The concentration of the ionic polymer (P) is concentrated to, for example, about 10 times that when the abrasive is used, and after mixing, it is diluted with water so as to have a specific concentration, and then used. <Polishing method> The polishing method according to the embodiment of the present invention is a method in which the polishing target is brought into contact with a polishing pad while the abrasive is supplied, and polishing is performed by a relative movement of the two. Here, the surface to be polished for polishing is, for example, a surface of a semiconductor substrate including a surface containing silicon dioxide. As a semiconductor substrate, the substrate for STI mentioned above is mentioned as a preferable example. The polishing method of the present invention is also effective for polishing the interlayer insulating film used in multilayer wirings in the manufacture of semiconductor devices. Examples of the silicon dioxide film in the STI substrate include a so-called PE-TEOS (a film formed by using tetraethoxysilane (TEOS) as a raw material and a plasma CVD (Chemical Vapor Deposition) method). Plasma Enhanced-TEOS. Further, as the silicon dioxide film, a so-called HDP (High Density Plasma) film formed by a high-density plasma CVD method can also be mentioned. Examples of the silicon nitride film include a film formed by using a low-pressure CVD method or a plasma CVD method using silane, dichlorosilane, and ammonia as raw materials. By using the abrasive of the present invention and polishing by the method described above, high planarity can be achieved. The evaluation of flatness is performed using, for example, a pattern wafer for STI. The polishing of the pattern for STI is preferably stopped at the point when the silicon nitride film is exposed, and the less the silicon nitride film of the pattern wafer is reduced, the more favorable the flatness is. Therefore, the reduction in the film thickness of the silicon nitride film can be used as an index of flatness. The smaller the thickness reduction of the silicon nitride film, the better the flatness. In the polishing method according to the embodiment of the present invention, a known polishing device can be used. Fig. 2 is a diagram showing an example of a polishing apparatus that can be used in the polishing method of the present invention. The polishing device 20 includes a polishing head 22 holding a semiconductor substrate 21 such as an STI substrate, a polishing platen 23, a polishing pad 24 attached to the surface of the polishing platen 23, and a polishing agent 24 for supplying the polishing agent 25 to the polishing pad 24. The abrasive supply pipe 26. It is configured as follows: while the abrasive 25 is supplied from the abrasive supply pipe 26, the polished surface of the semiconductor substrate 21 held by the polishing head 22 is brought into contact with the polishing pad 24, and the polishing head 22 and the polishing platen 23 are opposed to each other. Rotate to grind. The polishing apparatus used in the embodiment of the present invention is not limited to those having such a structure. The polishing head 22 can perform not only rotary motion but also linear motion. The polishing platen 23 and the polishing pad 24 may be the same size as or smaller than the semiconductor substrate 21. In this case, it is preferable to move the polishing head 22 and the polishing platen 23 relatively, so that the entire surface of the polished surface of the semiconductor substrate 21 can be polished. Furthermore, the polishing platen 23 and the polishing pad 24 may not be rotated, and may be moved unidirectionally, for example, by a conveyor system. The polishing conditions of such a polishing device 20 are not particularly limited. A load can be applied to the polishing head 22 and pressed against the polishing pad 24 to further increase the polishing pressure and increase the polishing speed. The polishing pressure is preferably about 0.5 to 50 kPa. From the viewpoint of uniformity, flatness, and prevention of scratches in the polished surface of the semiconductor substrate 21 at the polishing speed, the polishing pressure is more preferably 3 to 40 around kPa. The rotation speed of the polishing platen 23 and the polishing head 22 is preferably about 50 to 500 rpm, but it is not limited thereto. The supply amount of the abrasive 25 is appropriately adjusted according to the composition of the abrasive, the above-mentioned respective polishing conditions, and the like. As the polishing pad 24, a nonwoven fabric, a foamed polyurethane, a porous resin, a non-porous resin, or the like can be used. In order to facilitate the supply of the polishing agent 25 to the polishing pad 24, or to accumulate a certain amount of the polishing agent 25 on the polishing pad 24, the surface of the polishing pad 24 may be grooved, such as a grid, a concentric circle, or a spiral. In addition, if necessary, the pad adjuster is brought into contact with the surface of the polishing pad 24, and the polishing is performed while adjusting the surface of the polishing pad 24. According to the polishing method of the present invention, in a CMP process such as planarization of an interlayer insulating film or planarization of an STI insulating film in the manufacture of a semiconductor device, silicon oxide (such as silicon dioxide) can be contained at a higher polishing rate. The polished surface is polished, and a high selection ratio of the silicon oxide film and the silicon nitride film can be realized, thereby achieving higher flatness. [Examples] Hereinafter, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 15 are examples, and examples 16 to 20 are comparative examples. In the following examples, unless otherwise specified, "%" means mass%. The characteristic values were measured and evaluated by the following methods. [pH value] The pH value was measured using a pH meter HM-30R manufactured by Toya DKK. [Average secondary particle diameter] The average secondary particle diameter was measured using a laser scattering / diffraction type particle size distribution measuring device (manufactured by HORIBA, Ltd., device name: LA-920). [Polishing characteristics] The polishing characteristics were evaluated by using a fully automatic CMP polishing apparatus (manufactured by Applied Materials, apparatus name: Mirra) for the following polishing. The polishing pad was a double-layer pad (VP-3100 manufactured by Dow), and a CVD diamond pad adjuster (manufactured by 3M Company, trade name: Trizact B5) was used when the polishing pad was adjusted. The polishing conditions were set to a polishing pressure of 21 kPa, a rotation speed of the polishing platen to 77 rpm, and a rotation speed of the polishing head to 73 rpm. The supply rate of the abrasive was set to 200 ml / min. In order to measure the polishing speed, a blanket substrate with a silicon dioxide film obtained by using tetraethoxysilane as a raw material and forming a silicon dioxide film on an 8-inch silicon wafer by plasma CVD was used. A blanket substrate with a silicon nitride film obtained by forming a silicon nitride film on an 8-inch silicon wafer by CVD was used as an object to be polished. The film thickness of the silicon dioxide film and the silicon nitride film formed on the blanket substrate is measured using a film thickness meter UV-1280SE from KLA-Tencor. The polishing rate of the silicon dioxide film and the silicon nitride film was calculated by determining the difference between the film thickness before polishing of the blanket substrate and the film thickness after polishing for 1 minute. The average value of the polishing rate (Å / minute) obtained from the polishing rates at 49 points in the surface of the substrate was set as an evaluation index of the polishing rate. In addition, the ratio of the polishing speed of the silicon dioxide film to the polishing speed of the silicon nitride film (the polishing speed of the silicon dioxide film / the polishing speed of the silicon nitride film) was calculated as a selection ratio. [Example 1] A cerium oxide dispersion obtained by dispersing cerium oxide particles having an average secondary particle diameter of 120 nm in pure water (hereinafter, referred to as cerium oxide dispersion a) is the total mass of the cerium oxide particles relative to the abrasive After adding the content ratio (concentration) to pure water to 0.25%, tetrahydrofuran-2-carboxylic acid (hereinafter, referred to as "THF-C"), which is an organic acid having a monodentate ligand, was added to the content ratio. (Concentration) is added so that it is 0.10%, and polyoxyethylene diglyceryl ether (trade name: SC-E750, manufactured by Sakamoto Pharmaceutical Industry Co., Ltd., as polymer (2), p1 + q1 + r1 + s1 ≒ 13 in formula (2), Weight average molecular weight: 750) (hereinafter, referred to as nonionic polymer A. In Table 1, it is expressed as "polyoxyethylene diglyceryl ether (Mw750)". Mw means weight average molecular weight) in terms of the content ratio (concentration) It was added so that it might become 0.010%, and it stirred, and monoethanolamine (henceforth shown as MEA) was added, pH value was adjusted to 3.5, and the grinding | polishing agent (1) was obtained. [Examples 2 to 9] In the same manner as in Example 1, cerium oxide dispersion liquid a, tetrahydrofuran-2-carboxylic acid, and nonionic polymer A were added to pure water so that the content ratios (concentrations) shown in Table 1 may be obtained. While stirring, MEA was further added and adjusted to the pH value shown in Table 1, and abrasives (2) to (9) were obtained. [Example 10] In the same manner as in Example 1, cerium oxide dispersion liquid a, tetrahydrofuran-2-carboxylic acid, and polyglycerol (trade name: polyglycerol # 310), which is a polymer (1), were manufactured by Sakamoto Pharmaceutical Co., Ltd., Weight average molecular weight: 310) (hereinafter, referred to as non-ionic polymer B. In Table 1, it is expressed as "polyglycerol (Mw310)") and added to the pure substance such that the content ratio (concentration) shown in Table 1 becomes. Water was stirred, MEA was further added, and adjusted to the pH value shown in Table 1, and the abrasive | polishing agent (10) was obtained. [Example 11] In the same manner as in Example 1, cerium oxide dispersion liquid a, tetrahydrofuran-2-carboxylic acid, and polyoxypropylene diglyceryl ether (trade name: SC-P400) as a polymer (3) were prepared by Sakamoto Pharmaceutical Co., Ltd. Manufactured by the company, p 2 + q 2 + r 2 + s 2 ≒ 4 in formula (3), weight average molecular weight: 400) (hereinafter, referred to as nonionic polymer C. In Table 1, it is represented as "polyoxypropylene diglyceryl ether (Mw400)" Each of them was added to pure water so as to have the content ratio (concentration) shown in Table 1 and stirred, and then MEA was added to adjust the pH value shown in Table 1 to obtain an abrasive (11). [Example 12] A cerium oxide dispersion obtained by dispersing cerium oxide particles having an average secondary particle diameter of 100 nm in pure water (hereinafter, referred to as cerium oxide dispersion liquid b) is the total mass of the cerium oxide particles relative to the abrasive After adding the content ratio (concentration) to pure water to 0.25%, add tetrahydrofuran-2-carboxylic acid and polyoxyethylene diglyceryl ether (trade name: SC-E1000) as the polymer (2). Sakamoto Pharmaceutical Co., Ltd. Manufactured by the company, p1 + q1 + r1 + s1 ≒ 20 in formula (2), weight average molecular weight: 1000) (hereinafter referred to as non-ionic polymer D. In Table 1, it is expressed as "polyoxyethylene diglyceryl ether (Mw1000)") It was added to pure water with stirring so as to have the content ratio (concentration) shown in Table 1, and then MEA was added to adjust the pH value shown in Table 1 to obtain an abrasive (12). [Example 13] In the same manner as in Example 1, the cerium oxide dispersion liquid a, the N-acetamidoglycine and the nonionic polymer A, which are organic acids having a monodentate ligand, were shown in Table 1. The content ratio (concentration) was added to pure water and stirred, and then MEA was added to adjust the pH value shown in Table 1 to obtain an abrasive (13). [Example 14] A cerium oxide dispersion liquid (hereinafter, referred to as a cerium oxide dispersion liquid c) obtained by dispersing cerium oxide particles having an average secondary particle diameter of 170 nm in pure water was defined as the total mass of the cerium oxide particles relative to the abrasive. After adding the content ratio (concentration) to 0.25% to pure water, 2,2-bis (hydroxymethyl) propanoic acid and nonionic polymer A, which are organic acids with a single-dentate ligand, are respectively made into The content ratio (concentration) shown in Table 1 was added to pure water and stirred, and then MEA was added to adjust the pH value shown in Table 1 to obtain an abrasive (14). [Example 15] In the same manner as in Example 14, cerium oxide dispersion liquid c, DL-pyroglutamic acid, which is an organic acid having a single-dentate ligand, and nonionic polymer A were each contained as shown in Table 1. The ratio (concentration) was added to pure water and stirred, and then MEA was added to adjust the pH value shown in Table 1 to obtain an abrasive (15). [Example 16] In the same manner as in Example 1, cerium oxide dispersion liquid a, tetrahydrofuran-2-carboxylic acid, and polyvinyl alcohol (non-ionic polymers other than the non-ionic polymer (P)) were prepared as shown in Table 1. The content ratio (concentration) shown was added to pure water and stirred, and then MEA was added to adjust the pH value shown in Table 1 to obtain a polishing agent (16). [Example 17] In the same manner as in Example 14, cerium oxide dispersion liquid c and DL-pyroglutamic acid were added to pure water so as to have the content ratio (concentration) shown in Table 1, and stirred, and then MEA was added to adjust An abrasive (17) was obtained at the pH value shown in Table 1. [Example 18] In the same manner as in Example 1, cerium oxide dispersion liquid a and tetrahydrofuran-2-carboxylic acid were added to pure water so as to have the content ratio (concentration) shown in Table 1, and stirred, and then MEA was added to adjust it to The pH value shown in Table 1 was used to obtain an abrasive (18). [Example 19] In the same manner as in Example 1, cerium oxide dispersion liquid a, tetrahydrofuran-2-carboxylic acid, and nonionic polymer A were each added to pure water so as to have the content ratio (concentration) shown in Table 1 and carried out. After stirring, MEA was further added and adjusted to the pH value shown in Table 1 (pH outside the range of the abrasive of the present invention) to obtain an abrasive (19). [Example 20] As in Example 1, cerium oxide dispersion liquid a, polyacrylic acid and nonionic polymer A, which are organic acids other than organic acids having a single-dentate ligand, were made into the contents shown in Table 1, respectively. The ratio (concentration) was added to pure water and stirred, and then nitric acid was added to adjust the pH value shown in Table 1 to obtain an abrasive (20). The polishing characteristics (polishing speed of the silicon dioxide film, polishing speed of the silicon nitride film, and selection ratio) of the polishing agents (1) to (20) obtained in Examples 1 to 20 were measured by the methods described above. The measurement results are shown in Table 1. [Table 1] According to Table 1, the following conditions are known. That is, by using Example 1 containing cerium oxide particles as metal oxide particles, an organic acid having a single-dentate ligand, a nonionic polymer (P), and water, and having a pH value of 3.0 or more and 7.0 or less The abrasives (1) to (15) of -15 are polished to obtain a higher polishing rate for the silicon dioxide film. Moreover, it turns out that the selection ratio of a silicon dioxide film and a silicon nitride film becomes extremely high. On the other hand, it can be seen that the polishing agent (16) of Example 16 containing polyvinyl alcohol as a nonionic polymer but not the nonionic polymer (P), and Example 17 containing no nonionic polymer at all were used. In the case of the abrasive (17), the polishing rate of the silicon dioxide film was significantly lower than that of Examples 1 to 15. It is also known that the type of organic acid which does not contain a nonionic polymer at all and has a single-dentate ligand is different from the polishing agent (18) of Example 18 of Example 17, and contains an organic which does not have a single-dentate ligand. In the case of the organic acid of the acid, namely, the polishing agent (20) of Example 20 of polyacrylic acid, the selection ratio of the silicon dioxide film to the silicon nitride film was significantly lower than that of Examples 1 to 15. When the polishing agent (19) of Example 19 whose pH value was adjusted to 8.5 was used, agglomeration occurred, so that the polishing rate could not be evaluated. This application is based on Japanese Patent Application No. 2016-178507 filed on September 13, 2016, and the contents are incorporated herein by reference. [Industrial Applicability] According to the present invention, for example, in a CMP including a polished surface including a silicon oxide-containing surface, a sufficiently high polishing rate of the silicon oxide film can be maintained, and the polishing rate of the silicon nitride film can be maintained. The suppression is low, and a high selection ratio of the silicon oxide film and the silicon nitride film is achieved. Therefore, the polishing agent and polishing method of the present invention are better for planarizing the insulating film for STI in the manufacture of semiconductor devices.

1‧‧‧矽基板1‧‧‧ silicon substrate

2‧‧‧氮化矽膜2‧‧‧ Silicon Nitride Film

3‧‧‧溝槽3‧‧‧ groove

4‧‧‧二氧化矽膜4‧‧‧ Silicon dioxide film

20‧‧‧研磨裝置20‧‧‧Grinding device

21‧‧‧半導體基板21‧‧‧semiconductor substrate

22‧‧‧研磨頭22‧‧‧Grinding head

23‧‧‧研磨壓盤23‧‧‧Grinding platen

24‧‧‧研磨墊24‧‧‧ Abrasive Pad

25‧‧‧研磨劑25‧‧‧ Abrasive

26‧‧‧研磨劑供給配管26‧‧‧ Abrasive supply piping

圖1(a)及1(b)係表示於STI中藉由CMP進行研磨之方法之半導體基板的剖視圖。 圖2係表示可用於本發明之研磨方法之研磨裝置之一例的圖。1 (a) and 1 (b) are cross-sectional views of a semiconductor substrate showing a method of polishing by CMP in STI. FIG. 2 is a diagram showing an example of a polishing apparatus that can be used in the polishing method of the present invention.

Claims (10)

一種研磨劑，其特徵在於：其係含有金屬氧化物粒子、具有單牙配位基之有機酸、非離子性聚合物、及水，且pH值為3.0以上且7.0以下者，且上述非離子性聚合物包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。An abrasive, characterized in that it contains metal oxide particles, an organic acid having a single-dentate ligand, a nonionic polymer, and water, and the pH is 3.0 or more and 7.0 or less, and the nonionic The polymer includes at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether. 如請求項1之研磨劑，其中上述具有單牙配位基之有機酸係選自由具有雜環之單羧酸、碳數4以上且具有羥基之單羧酸、及具有胺基之單羧酸所組成之群中之至少1種。The abrasive according to claim 1, wherein the organic acid having a monodentate ligand is selected from a monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having 4 or more carbon atoms and a hydroxyl group, and a monocarboxylic acid having an amine group. At least one of the groups formed. 如請求項1或2之研磨劑，其中上述具有單牙配位基之有機酸之含有比率相對於研磨劑之總質量為0.003質量%以上且1.0質量%以下。The abrasive according to claim 1 or 2, wherein the content ratio of the organic acid having a single-dentate ligand to the total mass of the abrasive is 0.003 mass% or more and 1.0 mass% or less. 如請求項1至3中任一項之研磨劑，其中上述非離子性聚合物之含有比率相對於研磨劑之總質量為0.0002質量%以上且2.0質量%以下。The abrasive according to any one of claims 1 to 3, wherein the content ratio of the non-ionic polymer to the total mass of the abrasive is 0.0002 mass% or more and 2.0 mass% or less. 如請求項1至4中任一項之研磨劑，其中上述金屬氧化物粒子係氧化鈰粒子。The abrasive according to any one of claims 1 to 4, wherein the metal oxide particles are cerium oxide particles. 如請求項1至5中任一項之研磨劑，其中上述金屬氧化物粒子之平均二次粒徑為10 nm以上且500 nm以下。The abrasive according to any one of claims 1 to 5, wherein the average secondary particle diameter of the metal oxide particles is 10 nm or more and 500 nm or less. 如請求項1至6中任一項之研磨劑，其中上述金屬氧化物粒子之含有比率相對於研磨劑之總質量為0.01質量%以上且10.0質量%以下。The abrasive according to any one of claims 1 to 6, wherein the content ratio of the metal oxide particles to the total mass of the abrasive is 0.01% by mass or more and 10.0% by mass or less. 一種研磨方法，其係一面供給研磨劑一面使被研磨面與研磨墊接觸，藉由兩者之相對運動而進行研磨者，其特徵在於：使用如請求項1至7中任一項之研磨劑作為上述研磨劑，而對半導體基板之含有包含氧化矽之面之被研磨面進行研磨。A polishing method in which a polishing agent is supplied while contacting a surface to be polished with a polishing pad, and polishing is performed by a relative movement of the two, and is characterized in that the polishing agent according to any one of claims 1 to 7 is used As the polishing agent, a polished surface of a semiconductor substrate containing a surface containing silicon oxide is polished. 一種研磨用添加液，其特徵在於：其係用以與金屬氧化物粒子之分散液進行混合而製備研磨劑之添加液， 該添加液含有具有單牙配位基之有機酸、非離子性聚合物、及水，且pH值為3.0以上且7.0以下，並且上述非離子性聚合物包含選自由聚甘油、聚氧乙烯聚甘油醚及聚氧丙烯聚甘油醚所組成之群中之至少1種。An additive liquid for grinding, characterized in that it is an additive liquid for preparing an abrasive by mixing with a dispersion liquid of metal oxide particles, and the additive liquid contains an organic acid having a single-dentate ligand and nonionic polymerization. And water, and the pH value is 3.0 or more and 7.0 or less, and the non-ionic polymer includes at least one selected from the group consisting of polyglycerin, polyoxyethylene polyglyceryl ether, and polyoxypropylene polyglyceryl ether. . 如請求項9之研磨用添加液，其中上述具有單牙配位基之有機酸係選自由具有雜環之單羧酸、碳數4以上且具有羥基之單羧酸、及具有胺基之單羧酸所組成之群中之至少1種。The polishing additive according to claim 9, wherein the organic acid having a monodentate ligand is selected from a monocarboxylic acid having a heterocyclic ring, a monocarboxylic acid having 4 or more carbon atoms and a hydroxyl group, and a monocarboxylic acid having an amine group. At least one of the group consisting of a carboxylic acid.
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